Process for breaking petroleum emulsions



Patented a... 17, 1926.

UNITED STATES 1,59 ,5 ENT OFFICE.

MELVTN DE GBOOTE, OI ST. LOUIS,

MISSOURI, ASSIGNOR TO WM. S. BARNICKEL & COMPANY, OF WEBSTER GROVES, MIS

SO'U'RI, A CORPORATION OF MISSOURI.

rnocnss For. BREAKING PETROLEUM nmutsrons.

No Drawing.

This invention relates to the treatment of emulsions of a mineral oil and water, such as cut oil, roily oil, bottom settlings and other petroleum emulsions, for the purpose of separating the oil from the water.

Petroleum emulsions of the kind referred to are of the water-in-oil type and consists of droplets of water encased in emulsifying films and dispersed throughout a body .of 011 that constitutes the continuous phaseof the emulsion. They can be broken by subjecting them to the action of various kinds of chemical treating agents, such as those disclosed in United States Patents to William S. Barnickel, No. 1,223,660, dated April 24., 1917 and No. 1,467,831, dated September 11, 1923, the conventional process consisting in subjecting the emulsion to the action of a chemical substance or compound which acts on the emulsion in such a manner that the water of the emulsion will separate from the oil of the emulsion when the emulsion is allowed to remain in a quiescent state, at a suitable temperature, after treatment.

Intreating such emulsions it is essential for highly successful results that the treating agent reach the interfaces between the water droplets of the emulsion and the oil in which said droplets are dispersed, in order that the treating agent wi 1 act effectively on the emulsifying films t 'at encase the water drop- (lets, and the obj ect cure this desirable result, namely, insure the treating agent being segregated in relatively large uantities at the liquid-liquid interfaces 0 the emulsion.

To this end I propose to treat a petroleum emulsion of the water-in-oil type with an hydrophobe oil-soluble treating agent characterized by the fact that itis rendered dispersable as a coarse colloid in an oily vehicle, such as gasoline, kerosene or crude oil. Such a process is more effective than the usual process of treating a petroleum emulsion with an oil soluble hydrophobe treating agent in molecular dispersion,= due tothe fact that thecoarsely colloidal dispersion of the treating agent produces a materizll stronger segregation of the treating agen than can be obtained with a chemical-treating agent in molecular V persion of-the colloidal hydrophobe treatmg agent in oil is especially characterized by the of my. invention is to se-' Y at the liquid-liquid interfaces ofthe emulsiondispersion, ,The dis- Application filed May 29,1925. Serial No. 33,831.

fact that relatively concentrated dispersions of 2550% strength stay in a rather permanent dispersion, whereas, the weaker strength of 1-5 tend to settle out in a few hours.

I have found that the easiest way to obtain a coarse colloidal dispersion of an oilsoluble treating agent in a vehicle of the kind above mentioned is to add a liquid, such as glycerine, water, etc., ordinarily immiscible with the treating agent before said agent is mixed with the vehicle to produce a suitable dispersion. In so far as the two liquids to be mixed, that is, the agent and the glycerine, water, etc., are relatively immiscible, therefore, an oil soluble emulsifying agent such as calcium, or magnesium 'oleate will have to be added to the treating agent in order to render mixing or emulsification possible. This liquid, preferably water, is emulsified by any suitable means. The amount of water which I prefer to add So far as T have been ableto discover, any

oil-soluble hydrophobe chemical agent that is capable of use for breaking petroleum emulsions can be improved by the addition of sufficient immiscible liquid or water by the assistance of an emulsifyin to obtain a coarsely colloidal said treating agent in the vehicle used. My invention contemplates the use of a hydrated form of hydrophobe oil-soluble treating agent. Of the many suitable forms that can be used, such as naphthenic acids, rosins, fatty acids, etc., its has been found that the modified hydro hobe fatty acids described in the Barnickel atent No. 1, l67,831, dated September 11, 1923, are the most desirable. Such modified fatty acids are obtained by the action of certain chemical reagents on animal, vegetable and marine oils, and in producing such treating agents it has been found that those modifications obtained by a sulphonating agent, especially sulphuric acid on the following oils are most" suitable, namely, degras, horse, lard, neatsfoot, oleo, tallow, cod, herring,.menhaden, salmon, sardine, sperm, whale, castor,-China-wood, cocoanut, corn, cotton -seed, linseed,limbang, olive, palm, palm kernel, peanut, perilla, poppy seed, rape seed, sesame, soya bean, tea, red oil, as wellas the mixed fatty acids derived from the same or the purified fatty acids such as palmitic, oleic, stearic, ricinagent so as dispersion of iso-oleic sulphonic acid, hydroxy-stearic suladdition product.

phonic acid, di-hydroxy sulphonic acid, trihydroxystearic sulphonic acid, linolic sulphonic acid, ricinoleic sulphonic acid, lauric sulphonic acid, oleic sulphuric acid addition product, stearic sulphuric acid addition product, iso-oleic sulphuric acid addition product, hydroxystearic sulphuric acid addition product, di-hydroxy sulphuric acidaddition product, tri-hydroxystearic sulph'uric acid addition product, linolic sulphuric acid addition product, ricinoleic sul- 'phuric acid addition product, lauric 5111- phuric acid addition product, sulphated oil, Turkey-red oil, alizarine oil, soluble oil, dyeing oil, sulphonation products, fatty acid sulphonates, sulphoricinate, sulphonated oils, primary etheral salts of sulphuric acids,

ricinoleic sulphuric acid, di-hydroxystearosulphuric acid, di-basic di-ricinolelc acid,

monobasic di-ricinoleic acid, di-hydroxystearic acid, iso-ricinoleic acid, glycid acids,-

saturated lactone, saturated lactide, semisaturated di-rincinoleic acid, semi-saturated lactone, unsaturated lactide, polyricinoleic acids, oxy-stearic lactone, oleic acid sulphate,

,hydroxystearic acid, iso-oleic acid, paraoleic, elaidic acid and stearolactone, stearic acid hydrogen sulphate, hydroxystearo-sulphuric acid, sulpho-compound glycerides, hy-

droxylateld fatty acids, hydroxystearic acid, oxy-stear1c acid, linolenic sulphonic acid, sulpho-linolenic acid and linolenic sulphuric In the manufacture of these products by means of sulphuric acid, it is the usual practice to remove substantially all the sulphuric acid. This is not necessary in order to manufacture a treating compound, because the acidified mass is an active treatingagent. However, due to the corrosive effect of acid lines, it is usually deneutral or alkaline.

, t should be understood that the presence of a small amount of acid does not interfere with the employment of .bymy invention. A as a treating agen its employment in minute "beenthe practice where rosion'was not too great. Employingsulthis method of dehydration as contemplated The use of sulphuric acid has longbeen known and quantities has long therisk' from cor- P water of the compound will not separate from Consequently, the com-,

" employed by diluting the emulsion in any ound as employed be" in the Barnickel phuric acid in a nascent or an oil-soluble condition, such as its solution, in these treating agents, would be a desirable help.

I have found that hydrated, oil-soluble hydrophobe soaps can be used moreadvantageously than anhydrous materials, as the emulsifier for the treating agent and the liquid immiscible therewith, and accordingly, in practicing my invention I prefer to use hydrophobe, oil-soluble soap to the amount of about 10 to 20% dissolved in a modified fatty acid with the addition of approximately 2 to 20% of water. Previous reference has been made to the use ,of a suitable emulsifying agent, in order to obtain a mixture of the hydrophobe, oil-soluble treating agent and water, or other ordinarily immiscible liquid. Therefore, for obvious reasons, it is preferablethat the emulsifying agent be the hydrophobe soap of the chemical treating agent, thereby gaining the advantage of' the treating action of the soap, instead of an inert emulsifier, such as carbon black or rubber. Due to the stabilizing action of the oil soluble, hydrophobe soa the the treating agent. pound can be manufactured in large quantities and shipped in containers to the point Where it is to be used. The compound is best with an equal quantity of kerosene and adding the 50% solution to of the various ways now employed to bring a chemical treating agent into 'contact with a petroleum emulsion which it is desired to break, such, for example, as introducing thetreating agent into a conduit through which the emulsion is flowing, introducing the treating agentinto a tank in which the emulsion is stored, or introducing the treating agent into a roduc- Iing well in such a way that it can mix with the oil that is emerging from the ground before said oil and the water that emerges from the ground enter the barrel of the well pump or the tubing up through which said water and oil flow to the surface of the treatment the emulsion is ground. After allowed to stand in a quiescent state, at a so as to permit the passed through a hay tank, gun barrel or through a centrifugal or electrical dehydrator, and then allowed to stand in a quiescent state. pounds of the above materials, as disclosed Patent No. 1,467,831, previously referred to, are also suitable for this process. Generally, more of the above materials is used.

While I prefer to use a relatively concentrated solution, such as a solution of 25% The aromatic fatty acid com' a mixture of two or to 50% strength, my improved treating agent is characterized by its ability to form a coarsely-dispersed colloidal state, in dilute oil solution, and advantage of this property can be taken by using the treating agent directly, without intermediate solution, for treatin the emulsion, in so far as'it disperses 1n the continuousor oil phase of the emulsion.

In instances Where the treating agent that is used consists simply of a modified fatty acid mixed with a small quantity of water, it is often necessary to add to the com pound a material such as carbon black, asphalts, etcl, so as to prevent the water of the compound from separating. When such a stabilizing material is added the carbon black isfirst mixed with the modified fatty acid, and thereafter a small quantity of water is added to this mixture, the carbon black serving to eifectively prevent the water from separating before the compound is mixed with kerosene or any other suitable diluent to produce atreatingsolution.

Having thus described my invention, What 1 claim as new and desire to secure by Letters Patent is:

1. A process for treating water-in-oil emulsions, characterized by subjecting the emulsion to the action of an hydrophobe oil-soluble treating agent in which has been combined by the agency'of'a suitable emulsifier, a liquid that is immiscible with said treating agent. a a

2. A process for treating water-in-oil emulsions; characterized by subjecting the emulsion to the action of an hydrophobe oil-soluble treating agent in which has been combined water by the agency of a suitable 3. A process for treating water-in-oil emulsions, characterized by subjecting the emulsion to the action of an hydrophobe oilsoluble treating agent in which has been combined by the agency of an hydrophobe soap 2. liquid that isimmiscible with said treating agent. i

4. A process for treating Water-in-oil emulsions, characterized by subjecting the emulsion to the action of an hydrophobe oilsoluble treating agent in which has been combined water by the agency of an hydrophobe soap.

5. A process for treating water-in-oil emulsions, characterized by subjecting the emulsion to the action of anh drophobe oil-soluble, modified fatty acid, w ich bears a simple genetic relationship to the parentmaterial from which it was derived and in which has been combinedby the agency of a suitable emulsifier, a liquid that is immiscible with said acid.

6. A process for treating water-in-oil emulsions, characterized by subjecting the emulsion to the action of an hydrophobe oil soluble modified fatty acid, which bears a simple genetic relationship to the parent material from which it was derived and in which has been ,combined water by the agency of a suitable emulsifier.

7 A process for treating water-in-oil emulsions, characterized by subjecting the emulsion to the action of an hydrophobe oilsoluble modified fatty acid, which bears a simple genetic relationship to the parent material from which it was derived and in which has been combined by the agency of 'an hydrophobe soap, a liquid that is immiscible with said acid.

81A process -for treating water-in-oil emulsions, characterized by subjecting the emulsion to the action of an hydrophobe oil-soluble modified fatty acid, which bears a simple genetic relationship to the parent material from which itv was derived and in which has been combined water by the agency of an hydrophobe soap.

, B ELVIN DE GROOTE. 

